Emulsion



FIPSSU? Patented July 11,1933

UNITED STATES BENJAMIN R. HARRIS,

OF CHICAGO, ILLINOIS EMULSION No Drawing.

My invention relates in general to improved emulsions and emulsion improving substances. It relates more specifically to an improved non-spattering type of margarine and anti-spattering substances for use with margarine and is a continuation in part of application Serial N 0. 476,935 filed August 21, 1931. The latter application is a division of application Serial No. 475,622, filed August 15, 1930 as a continuation in part of application Serial No. 383,143 filed August 2, 1929.

By means of my new products I am able to impart superior qualities to many types of emulsions, particularly to emulsions of fats and oils used for culinary purposes, but I shall explain the invention in connection with improvements in margarine. Those skilled in the art are referred to my co-pending application, Serial Number 566,156, filed September 30, 1931, as a continuation in part of application Serial No. 47 5,622 for a more complete disclosure of certain details of the invention than is made herein. In general the present invention represents a specific embodiment of the main invention disclosed in the co-pending application above referred to, and while the present disclosure issubstantially complete insofar as it describes the invention, and supports the claims, those interested in the art are referred to the co-pending case for a more complete disclosure of the basic concept of the invention.

The principal object of my present in- Vention is to improve such forms of emulsion as margarine. I

Another object is to reduce the spattering of margarine when used for frying purposes and generally improve its frying behavior.

Other objects and features of the invention will be apparent from a consideration of the following detaileddescription.

As was disclosed in my co-pending applications I have discovered a large class of chemical compounds which may be used to impart improved characteristics to all types of water-oil emulsions, particularly those used for cooking purposes, and other types of culinary fat preparations. These substances have several characteristics in common which make them very valuable in their use with margarine. These substances are compatible with mild acids and in particularwith lactic acid in the concentration and under the conditions existing in margarine. They are in Serial No. 586,159.

- the water or oil phase. These substances are semi-colloidal or truly colloidal in character and are frequently colloidal ly'dispersible in aqueous and/or oleaginous media. They are, moreover, substantially non-volatile at margarine frying temperatures and so will remain in the margarine and perform their function during frying.-

()ne of the most important characteristics Search Room of these compounds is the presence in the molecule of the two types of groups in bal anced relation to each other, one group being hydrophyllic or Water wetting in character, and the other group being lipophyllic or fat wetting in character; These groups must exist in the molecule in such a state of balance that they will function at the water-oil interface in the intended manner. Presumably these-substances orientate themselves at the interface, by reason of the balance of the two types of groups, but it is understood that the invention does not depend upon this explanation.

My co-pending application treats exhaus tivcly of the manner in which the balance between the two groups may be determined so that without tests of any kind it is possible for the skilled colloid chemists to pick out compounds which cannot function efi'ectively as anti-spatterers, as well as compounds which clearly will be effective as anti-spatterers.

However, there are compounds of such character that the state of balance existing between the two groups in the molecule is preferably determined by a simple quick test.

The balance of the hydrophile-lipophile groups in the compounds which I apply in my invention is one of the characteristics and determinants of the class of substances which I employ.

The test which I have chosen as a means for determining the hydrophile-lipophile spoon test. It is carried out as follows: From 0.05 to 0.50 gr. of the material or sub Stance in question is introduced into a porcelain mortar, wetted and ground into a smooth paste or solution with a pestle with a minimum proportion of water; two to five drops generally will sufiice.

An ordinary margarinesuch for example as one made from vegetable oils, and fats and cultured skimmed milk and which possesses the usual property of spattering during frying is selected. Ten grams of this margarine are then introduced in small portions into the mortar and macerated thoroughly with the paste first prepared until the entire ten gram portion is thoroughly and uniformly intermixed with the material in the mortar. Two grams of this mixture are introduced into a tablespoon and held directly over a free flame such for example as a Bunsen flame, one or two inches long, in such a position that the point of the flame just about reaches the bottom of the spoon. A clean sheet of paper is placed on the bottom of the burner by inserting the stem of the Bunsen burner prior to lighting through a hole made in the center of. the paper and v allowing the paper to drop to the base of the burner to catch the margarine splashed out during the heating. The mixture in the spoon is heated until all of the water is boiled 011' and the ebullition ceases and the spots on the paper observed.

If this treated margarine spots the paper to the same extent as the untreated margarine from which the former was prepared, then the lipophile and hydrophile groups of the compound are not balanced. The number and size of spots on the paper or added weight can be readily determined.

If the increase in weight of the paper or the number and character of the spots produced on the paper up until all the water has boiled ofi are less than that produced by similarly heating two grams of the original untreated margarine employed for the test, then the material or substance in question has balanced hydrophile-lipophile groups. The expression balanced lipophile and hydrophile groups used in the claims is .to be interpreted in terms of the above doing compounds of the present invention are entirely non-nitrogenous, but if they contain any nitrogenous group, it should be devoid of the nitrogenous linkage expressed in the following formula Roon In my co-pending application, Serial No. I

566,158, filed September 30, 1931, I describe and claim certain types of nitrogenous compounds which can be used with my invention. In my present application I am interested principally in compounds containing phosphorus.

Examples of some of the phosphatic materlals which I have used as anti-spattering agents, many of them not known heretofore, are as follows:

. 0 1 v I O11H15-i30OH CH -0OH CH -O-i-0H (Stearyl dlethylene glycol dlhydrogen orthophosphate) drophyllic phosphorus containing radical or its metal derivative with a lipophile group will give an anti-spatterer.

Examples of molecules, with phosphorus containing hydrophile groups as well as lipophile groups, but which nevertheless are not anti-spatterers are as follows:

Gl s A In the case of compounds of both class A and class B, anti-spattering powers are lacking because of inadequate balance between the lipophile and hydrophile groups. In the case of compounds of class A, the hydrophile group dominates and is inadequately balanced y the lipophile roup, that is, the lipophile characteristicso the latter are too weak to adequately balance and coact with the hydrophile group. In the case of substances of class B, the reverse situation exists and anti-spattering power is absent because the lipo hile group is dominant and is inadequately balanced by the hydrophile group.

The examples of hosphatic anti-spatterers listed above, as well as other phosphatic substances which can be employed for the purpose which I have used successfully, I prepared by a number of different methods which are adequately described in the scientific and technical literature, and which methods are readily available to skilled chemists.

The compounds described above are of unusual importance in connection with their use with water-oil emulsions for all kinds, but they have a particular adaptation for use with all culinary emulsion products such as margarine. Commercial margarine after being treated with my anti-sputtering agent, when fried in a pan exhibits improved frying behavior in that it allows its water to boil off quietly, fries in a pleasing and comparatively quiet manner with the formation of considerable turbid froth and foam after the manner of butter, reduces the tendency of the curd to stick to the bottom of the frying pan,and reducesthe amountof material whic escapes from the pun by spattering. Untreated margarine on the other hand when fried bumps turbulently, sputters noisily and foams comparatively little. Also what little foam there is, is transparent and of an entirely different character from that obtained from margarine previously treated with an antispatterer.

My emulsion improvers may be introduced in the margarine in a number of ways, as long as a satisfactory dispersion is obtained. For instance, the main constituents of margarine are edible oils and fats and cultured milk, and the anti-spattering or improving compounds may be introduced either into the oils or milk in any suitable manner. They may also be introduced into the churn durin the production of the emulsion in its liqui state, care being taken to brin about the necessary dispersion. Or, the antl-s attering material may be used in a dry condition and mixed with the salt which is worked into the crystallized margarine, or the anti-spattering material may be made into a paste with the milk and kneaded in, or blended into the margarine.

Generally speaking, the compoundswhich I am using in connection with this invention are: hosphoric acid esters of hi h molecular weig t organic compounds WlllCh will balance the phosphoric acid radical. It is to be noted that in each case, in the examples given above, the phosphorus containing hydrophile group is at or near an end of the molecule. These com ounds may be represented structurally as ollows inwhich O is oxygen, P is phos horns, X is an edible cation such as hydro en, sodium, potassium, calcium, or the like, a is either an edible cation or an organic radical, and R is an organic lipophile group, and w a whole number.

Thus the above compounds may be phosphoric acid esters of a high molecular alcohol such as cetyl alcohol, or it may be a phosphoric acid ester of a polyalcohol and/or its substitution products such as, for example, a phosphoric acid ester of glycol or diethylene glycol in which one OH is esterified with a higher fatty acid such as'stearic acid, or com- ZbZ. UUMIUSI l IUNS,

. bined in an ether linkage with a high alcohol such. as cholesterol. Thus for example, a phosphoric acid ester of stearyl. diethylene v glycol, a phosphoric acid ester of monostearyl glycerol, or a phosphoric acid ester of cholester l-cliethylene glycol.

t must not be inferred from the preceding part of this specification that every antispattering substance of the character herein disclosed must be insoluble in oleaginous and/or aqueous media. It is true that the greater number of anti-spattering compounds of the present invention are substantially insoluble in these media, but there are a limited number of water soluble compounds which if used in sufliciently larger proportions may have an effect in reducing spattering during frying.

It appears that in a given homologous series, there is a point or range at which lipophile and hydrophile characteristics are so balanced that an optimum power for the prevention of spattering is imparted to the molecule. Going from this point higher in the series, in the direction of increasing molecular weight in the lipophile group with a given phosphate group, the anti-sputtering power diminishes, because of excessive lipo-' phile'characteristics in the molecule; going down from this point or range lower in the series, anti-spattering power again diminishes, because of the excessive hydrophile characteristics in the molecule; the tendency. to dissolve in water concurrently increases. In certain homologous series, however, there are cases of water soluble substances which can function as anti-spatterers. Examples of water soluble phosphorus compounds which may be used as anti-spatterers are In general it is true, other things being equal, that a water soluble substance is not as effective as one that is not freely soluble in water. It is also true that the total number of available anti-spatterers not soluble in water is greater than the number of soluble ones. This is apparent from the following consideration. Generally, water solubility is negligiblein a'nti-spatterers with a relatively large number of carbons in the lipophile group. However, below ten or twelve carbons, for example, the tendency for solubility in water gradually increases and in the range, fourto seven or eight carbons, the antispatterers are generally freely soluble in water. Below four carbons, almost invariably, the lipophile group is too weak to balance the hydrophile group and anti-spattering power is absent. It is evident therefore, that the total number of possible freely waa suave MMUU ter soluble anti-spatterers is small as compared with the total number of possible antispatterers not soluble in water.

In descending in any given homologous, anti-spattering series there is a gradual transition, and the change in any one carbon interval is not great, there is a gradual diminishing from the optimum downward, and finally, very low in the series, anti-spattering power vanishes.

As to the specific application of the invention to margarine and other emulsions or oleaginous culinary preparations, it is clear that since there are many phosphatic compounds containing balanced hydrophile and lipophile groups, it is impractical and un-' necessary to list each particular combination Search Roorr of groups which can be used in accordance with my invention. Moreover, while I leave something to the skill of persons applying my invention, my description is wholly sufiiciently exhaustive, particularly when considered with respect to my prior applications,

to enable those skilled in the art to successfully practice the same.

The term non-spattering margarine as used in the claims is employed to designate a margarine, the frying behavior ofwhich is improved by the additon thereto of the novel materials of my invention herein described to reduce spattering.

The term margarine as emplo ed in the claims includes plastic emulsions o vegetable or animal oleaginous substances or mixtures thereof, with aqueous materials such as water, sweet or ripened milk, and with or without coloring matter or other addition agents.

What I claim as new and desire to protect by Letters Patent of the United States is:

oleaginous media and aqueous media and having included therein a proportion of a non-nitrogenous chemical compound characterlzed by a coactlon in its molecule of balanced lipophile and hydrophile groups, and represented by the structure 1. A non-spattering margarine including tarmac having included therein a proportion of a non-nitrogenous compound in the form of a phosphoric acid ester of a derivative of glycerine of high molecular wei ht, said compound having balanced lipopliile and hydrophile groups.

4. A 11on spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a non-nitrogenous substance in the form of a phosphoric acid ester of a glycol derivative, said compound having balanced lipophile and hydrophile groups.

5. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a non-nitrogenous substance in the form of a phosphoric acid ester of a higher fatty acid glycerol derivative, said compound having balanced lipophile and hydrophile groups.

6. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a non-nitrogenous substance in the form of a phosphoric acid ester of a higher fatty acid glycol derivative, said compound having bal anced lipophile and hydrophile groups.

7. A non-spattering margarine having an oleaginous phase and an aqueous phase, having included therein a phosphoric acid ester of astearic acid ester of glycol, said phosphoric acid ester having balanced lipophile and hydrophile groups.

8. A non-spattering margarine having an oleaginous phase and an aqueous phase, and a proportion of a phosphoric acid ester of stearyl diethylene glycol, said phosphoric acid having balanced lipophile and hydrophile groups.

9. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having a proportion of a non-nitrogenous phosphoric acid ester of a higher aliphatic derivative of glycerine, said phosphoric acid ester having balanced lipophile and hydrophile groups.

10. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a non-nitrogenous phosphoric acid ester having balanced lipophile and hydrophile groups.

11. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having a proportion of a non-nitrogenous phosphoric acid ester of monostearyl glycerol, said phosphoric acid ester having balanced lipophile and hydrophile groups.

12. A non-spattering margarine having an oleaginous phase and an aqueous phase. and having included therein a phosphoric acid ester of cholesteryl diethylene glycol, said phosphoric acid ester having balanced lipophile and hydrophile groups.

13. A non-spattering margarine having an oleaginous phase and an aqueous phase, and

having included therein a sodium salt phosphoric acid ester of palmityl alcohol, said phosphoric acid ester having balanced lipophile and hydrophile groups.

14. A non-sputtering margarine containing an oleaginous phase and an aqueous phase and having included therein a proportion of an improving agent comprising a non-nitrogenous substance characterized by a coaction in its molecule of balanced lipophile and hydrophile groups, and in which the hydrophile function is imparted to the molecule primarily by a group containing phosphorus.

15. A non-spattering margarine containing an oleaginous phase and an aqueous phase and having included therein a proportion of an improving agent, comprising a non-nitrogenous substance, characterized by co-action in its molecule of balanced lipophile and hydrophile groups and represented by the structure Heal X Y5 w ture o {n-o-t-o-} x Y()/ in in which 0 is oxygen, P is phosphorus, X is an edible cation, Y is either an edible cation or an organic radical, w is a. whole number, and R is a lipophile alkyl radical including an ester group.

17 A non-spattering margarine containing an oleaginous phase and an aqueous phase and having included therein a proportion of an improving agent comprising a non-nitrogenous substance, characterized by co-action in its molecule of balanced lipophile and bydrophile groups and represented by the strucin which 0 is oxygen, P is phosphorus, X is an edible cation, Y is either an edible cation or an organic radical, w is a small Whole number, and R is a lipophile radical including an ester or an ether group.

18. A non-spattering margarine including an oleaginous phase and an aqueous phase,

252. COMPOSITIONS,

and having included therein a proportion of a water soluble non-nitrogenous substance characterized by balanced lipophile and hydrophile groups, and represented by the forin which 0 is oxygen, P is" phosphorus, X is an edible cation, Y is either an edible cation or an organic radical, and R is an organic lipophile radical with at least four carbon atoms, and w is a small whole number.

' mula 19. A non-spattering margarine including an oleaginous phase and an aqueous phase, and having included therein a relatively small amount of monobutyl disodium phosphate CH;CH:'CH:OH:'OP=O I ONa Na 20. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a non-nitrogenous water soluble substance characterized by a coaction in its molecule of balanced lipophile and hydrophile groups,

in which the lipophile group has at least four carbons, and wherein the hydrophile function is imparted to the molecule primarily by a group containing phosphorus.

21. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous chemical compound characterized by a coaction in its molecule of balanced lipophile and hydrophile groups, and

represented by the structure i lipophile group being a non-aromatic relatively high molecular weight radical.

23. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of anon-nitrogenous compound in the form of a phosphoric acid ester of a derivative of glycerine of high molecular weight, said compound having balanced lipophile and hydrophile groups, the lipophile group being a non-aromatic relatively high molecular weight radical.-

Search 24. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous substance in the form of a phosphoric acid ester of a glycol derivative, said compound having balanced lipophile and hydrophile groups.

25. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous substance in the form of a phosphoric acid ester of a higher fatty acid glycerol derivative, said com ound having balanced lipophile and hydrop ile groups.

26. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous substance in the form of a Room phosphoric acid ester of a higher'fatty acid glycol derivative, said compound having balanced lipophile and hydrophile groups.

27. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous phosphoric acid ester of a higher aliphatic derivative of phosphoricv acid ester having alanced lipophile and hydrophile groups.

. 28. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous substance characterized by coaction in its molecule of balanced lipophile and hydrophile groups, and represented by the structure 0 this].

in which 0 is o n P is h horns X is an edible ziiiml, Y i; Sitar ari edible cation or an organic radical, 'w is a small whole number, and R is an organic non-aromatic relatively high molecular weight lipophile group.

29. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous substance, characterized by a coaction in its molecule of balanced lipophile and hydrophile groups and represented by the structure in which 0 is o n, P is phosphorus. X is an edible da t ion, Y is either an edible cation or an organic radical, w is a whole number, and R is a lipophile alkyl radical including an ester group.

30. An emulsion including an oleaginous phase, an aqueous phase, and a proportion of a non-nitrogenous substance, characterized by coaction in its molecule of balanced lipophile and hydrophile groups and represented by the structure glycerine, said ios in which 0 is oxygen, P is phosphorus,

X is an edible cation, Y is either an in which 0 is oxygen, P is phosphorus, X is an edible cation, Y is either an edible cation or an organic radical, R is an organic non-aromatic relatively high molecular weight lipophile radical with at least four carbon atoms, and wiis a small whole number.

In witness whereof, I hereunto subscribe my name this 26 day of'Sept., 1931.

BENJAMIN R. HARRIS. 

